Curable coating vehicle based upon aminoalkyloxy silanes and organic isocyanates

ABSTRACT

Disclosed is an ungelled resin comprising a compound corresponding to a specified formula (I) which compound typically is prepared by reaction of an aminoalkyloxy silane with an organic isocyanate. The ungelled resin contains a hydrolyzable group that is attached directly to Silicon. The ungelled resin can be utilized in coating compositions. The ungelled resin can be cured with moisture and/or with polyols, and can be used to provide protective and/or decorative films on a variety of substrates. 
     The novel compounds contained in the ungelled resin for convenience can be thought of as prepared from an organic isocyanate having an average functionality of at least 1; a silicon-containing compound corresponding to a specified formula (III) infra, the silicon-containing compound having at least one hydrolyzable group; and a compound containing at least 2 carbon atoms, at least 1 functional group reactive with a moiety on the silicon-containing compound and at least one amino group. A compound of the resin contains at least one hydrolyzable group from the silicon-containing compound. A compound of the resin also contains a residue of the silicon-containing compound bonded to a residue of the compound containing at least 2 carbon atoms through an oxygen-silicon linkage.

BACKGROUND OF THE INVENTION

The present invention is directed to new resins which may be utilized incoating compositions and to coating compositions containing the resins.In particular, the invention is directed to resins which can be curedwith moisture and/or with polyols, and which can be used to provideprotective and/or decorative films on a variety of substrates, whichfilms exhibit an excellent combination of physical and chemicalproperties.

SUMMARY OF THE PRESENT INVENTION

A resin of the invention is ungelled and comprises a compound which forconvenience can be thought of as prepared from an organic isocyanatehaving an average functionality of at least 1; a silicon-containingcompound corresponding to a specified formula (III) infra, thesilicon-containing compound having at least one hydrolyzable group; anda compound containing at least 2 carbon atoms, at least 1 functionalgroup reactive with a moiety on the silicon-containing compound and atleast one amino group. A compound of the resin contains at least onehydrolyzable group from the silicon-containing compound. A compound ofthe resin also contains a residue of the silicon-containing compoundbonded to a residue of the compound containing at least 2 carbon atomsthrough an oxygen-silicon ##STR1## linkage.

The invention is also directed to a coating composition comprising aresin of the invention.

DETAILED DESCRIPTION OF THE INVENTION

An ungelled resin of the invention comprises a compound corresponding tothe following formula (I), ##STR2## wherein Q represents the residue ofan organic isocyanate having an average isocyanate functionality of atleast 1,

R¹ independently represents H, a C₁ to C₁₀ alkyl radical, a C₁ to C₁₀hydroxyalkyl radical, or a radical corresponding to the formula ##STR3##wherein Z represents H or C₁ to C₄ alkyl, and W represents ##STR4## inwhich R⁸ represents C₁ to C₈ alkyl, X represents a divalent radicalcontaining at least 2 carbon atoms optionally containing one or moregroups selected from ether, amino, amido, carbamate, urea, and thio,

A Represents a monovalent silicon-containing group corresponding to theformula ##EQU1## wherein R² independently represents hydrogen, a C₁ toC₁₀ alkyl group, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ aryl group,or a monovalent aminoalkyl group, that is directly attached to Si,

Y represents a hydrolyzable group that is attached directly to Si,

m is an integer ranging from 1 to 5,

e is a positive integer wherein 1≦e≦11, d is zero or a positive integerwherein 0≦d≦10, and 3≦d+e≦11, and

wherein x is a positive number which is equal to or less than theaverage isocyanate functionality of said organic isocyanate.

Examples of the hydrolyzable groups, Y, include ##STR5## and the C₂ toC₃ residue of a 1,2- or a 1,3-glycol wherein R³ represents C₁ -C₇ alkyl,C₆ -C₈ cycloalkyl, C₆ -C₈ aryl, or C₃ -C₈ alkoxyalkyl,

R⁴ represents H or C₁ -C₄ alkyl,

R⁵ and R⁶ independently represent C₁ -C₄ alkyl, C₆ -C₈ cycloalkyl, or C₆-C₈ aryl, and

R⁷ represents C₄ -C₇ alkylene.

It is preferred that the aforesaid monovalent silicon-containing group(formula II) in a resin of the invention contain at least 2 of thehydrolyzable groups Y which may be the same or different.

In formula (I) defined above, R¹ preferably is H or C₁ to C₁₀ alkyl.

A coating composition of the invention comprises an ungelled resin ofthe invention.

An organic isocyanate for preparing a resin of the invention essentiallycan be any organic isocyanate having an isocyanate functionality of atleast 1, preferably greater than 1.8, most preferably equal to orgreater than 2. The organic isocyanate can be a single compound or amixture of compounds. It is to be understood that when a mixture oforganic isocyanate compounds is employed, the isocyanate functionalityreferred to above is an average isocyanate functionality determined forthe mixture. The organic isocyanate can be an isocyanate-terminatedprepolymer prepared by the generally known prepolymer technique in whicha polyol and polyisocyanate are reacted in relative proportions toproduce an isocyanate-terminated prepolymer. Also, mixtures of organicisocyanate prepolymers with monomeric isocyanates (so-calledsemi-prepolymers) may be employed in the prepolymer technique.

Examples of organic isocyanates for preparing a resin of the inventioninclude aromatic, aliphatic, cycloaliphatic, and heterocyclicisocyanates and they may be unsubstituted or substituted with groupssuch as halogen, etc. Many such organic isocyanates are known, specificexamples of which include: toluene-2,4-diisocyanate,toluene-2,6-diisocyanate, and mixtures thereof;diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate andmixtures thereof; p-phenylene diisocyanate; biphenyl diisocyanate;3,3'-dimethyl-4,4'-diphenylene diisocyanate;tetramethylene-1,4-diisocyanate; hexamethylene-1,6-diisocyanate;2,2,4-trimethylhexane-1,6-diisocyanate; lysine methyl esterdiisocyanate; bis(isocyanatoethyl)fumarate; isophorone diisocyanate;ethylene diisocyanate; dodecane-1,12-diisocyanate;cyclobutane-1,3-diisocyanate; cyclohexane-1,3-diisocyanate,cyclohexane-1,4-diisocyanate and mixtures thereof; methylcyclohexyldiisocyanate; hexahydrotoluene-2,4-diisocyanate,hexahydrotoluene-2,6-diisocyanate and mixtures thereof;hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanateand mixtures thereof; perhydrodiphenyl-methane-2,4'-diisocyanate,perhydrodiphenylmethane-4,4'-diisocyanate, the isocyanurate ofisophorone diisocyanate (available as T-1890 from Veba Chemie), thebiuret of hexamethyl diisocyanate (available as DESMODUR-N from MobayChemical Corp.), and mixtures thereof.

In a preferred embodiment of the invention, an isocyanate-terminatedprepolymer which is a reaction product of an organic polyisocyanate andone or more polyols having an average molecular weight ranging from 62to about 3,000 is utilized as the organic isocyanate to provide aresidue symbolized by Q in formula (I) above. In this embodiment, it isparticularly preferred that the polyol component for preparation of theisocyanate-terminated prepolymer comprise a polyol containing at leastone carboxylic acid group, optionally in combination with a monohydricalcohol containing a carboxylic acid group. For this purpose, varioushydroxy acids can be employed including such compounds as dimethylolpropionic acid, 2,4,6-trihydroxybenzoic acid,4,4-bis(4-hydroxyphenyl)-pentanoic acid, and the like, optionally incombination with hydroxy acids such as hydroxyacetic acid, beta-hydroxypropionic acid, alpha-hydroxy butyric acid, mandelic acid, hydroxycaproic acid, and the like. Examples of organic isocyanates suitable forpreparing the isocyanate-terminated prepolymer include any of organicisocyanates described previously for preparing a resin of the invention.

Examples of polyols suitable for preparation of isocyanate-terminatedprepolymers include polyols in the broad classes including: simplediols, triols, and higher hydric alcohols; polyester polyols optionallymodified with a fatty acid; polyether polyols; amide-containing polyols;and polyurethane polyols.

The simple diols, triols, and higher hydric alcohols useful in thepreparation of the isocyanate-terminated prepolymers are generallyknown, examples of which include: ethylene glycol; propylene glycol;1,2-butanediol; 1,4-butanediol; 1,3-butanediol;2,2,4-trimethyl-1,3-pentanediol; 1,5-pentanediol; 2,4-pentanediol;1,6-hexanediol; 2,5-hexanediol; 2-methyl-1,3-pentanediol;2-methyl-2,4-pentanediol; 2,4-heptanediol; 2-ethyl-1,3-hexanediol;2,2-dimethyl-1,3-propanediol; 1,4-cyclohexanediol;1,4-cyclohexanedimethanol; 1,2-bis(hydroxymethyl)cyclohexane;1,2-bis(hydroxyethyl)cyclohexane;2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate;dipropylene glycol; the alkoxylation product of 1 mole of2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol-A) and 2 moles ofpropylene oxide available as DOW-565 from Dow Chemical Company; and thelike.

Polyester polyols useful in the preparation of isocyanate-terminatedprepolymers are generally known and are prepared by conventionaltechniques utilizing simple diols, triols and higher hydric alcoholsknown in the art including but not limited to the previously describedsimple diols, triols, and higher hydric alcohols (optionally incombination with monohydric alcohols) with polycarboxylic acids. In aparticularly preferred embodiment of the invention, the polyester polyolhas an average molecular weight ranging from about 170 to about 2,000.Examples of suitable polycarboxylic acids include: phthalic acid,isophthalic acid, terephthalic acid; trimellitic acid;tetrahydrophthalic acid, hexahydrophthalic acid; tetrachlorophthalicacid; adipic acid, azelaic acid, sebacic acid; succinic acid; malicacid; glutaric acid; malonic acid; pimelic acid; suberic acid;2,2-dimethylsuccinic acid, 3,3-dimethylglutaric acid;2,2-dimethylglutaric acid; maleic acid; fumaric acid; itaconic acid; andthe like. Anhydrides of the above acids, where they exist, can also beemployed and are encompassed by the term "polycarboxylic acid." Inaddition, certain materials which perform in a manner similar to acidsto form polyester polyols are also useful. Such materials includelactones such as caprolactone, propylolactone and methyl caprolactone,and hydroxy acids such as hydroxy caproic acid and dimethylol propionicacid. If a triol or higher hydric alcohol is used, a monocarboxylicacid, such as acetic acid and benzoic acid, may be used in thepreparation of the polyester polyol, and for some purposes, such apolyester polyol may be desirable. Moreover, the term polyester polyolsas used herein is intended to encompass polyester polyols optionallymodified with fatty acids or glyceride oils of fatty acids (i.e.,conventional alkyd polyols containing such modification).

Examples of the optional monohydric alcohols which may be used toprepare the polyester polyols include: ethanol, propanol, isopropanol,n-pentanol; neopentyl alcohol; 2-ethoxyethanol; 2-methoxyethanol;1-hexanol; cyclohexanol; 2-methyl-2-hexanol; 2-ethylhexyl alcohol;1-octanol, 2-octanol, 1-nonanol; 5-butyl-5-nonanol; isodecyl alcohol;and the like.

Polyether polyols which may be used in the preparation ofisocyanate-terminated prepolymers are generally known. Examples ofpolyether polyols include the poly-(oxyethylene) glycols andpoly(oxypropylene) glycols prepared by the acid or base catalyzedaddition of ethylene oxide and/or propylene oxide to ethylene glycol,propylene glycol or dipropylene glycol initiators and by thecopolymerization of propylene oxide and ethylene oxide with initiatorcompounds such as trimethylolpropane, glycerol, pentaerylthritol,sorbitol, sucrose and the like. The polyether polyols also include thegenerally known poly(oxytetramethylene) glycols prepared by thepolymerization of tetrahydrofuran in the presence of Lewis acidcatalysts such a boron trifluoride, tin (IV) chloride, antimonypentachloride, antimony trichloride, phosphorous pentafluoride, andsulfonyl chloride. Other examples of polyether polyols include thegenerally known reaction products of 1,2-epoxide-containing compoundswith polyols such as those included in the description of simple diols,triols, and higher hydric alcohols above.

Amide-containing polyols are generally known and typically are preparedfrom any of the above-described diacids or lactones and diols, triolsand higher alcohols, and diamines or aminoalcohols as illustrated, forexample, by the reaction of neopentyl glycol, adipic acid andhexamethylenediamine. The amide-containing polyols also may be preparedthrough aminolysis by the reaction, for example, of carboxylates,carboxylic acids, or lactones with aminoalcohols. Examples of suitablediamines and amino-alcohols include hexamethylenediamine,ethylenediamine, phenylenediamine, toluenediamine; monoethanolamine,diethanolamine, N-methyl-monoethanolamine, isophoronediamine,1,6-menthanediamine and the like.

Polyurethane polyols are generally known. Polyurethane polyols can beproduced by reacting any of the above-described polyols, includingdiols, triols, and higher alcohols, polyester polyols, polyetherpolyols, and amide-containing polyols with an organic polyisocyanate.The organic polyisocyanate may be reacted with the polyol eitherdirectly to form the polyurethane polyol or by the generally knownprepolymer technique wherein the polyol and polyisocyanate are reactedin relative proportions to first produce an isocynate-terminatedprepolymer with subsequent reaction to the prepolymer with additionalpolyol to form the polyurethane polyol. Also, mixtures of organicisocyanate prepolymers with monomeric isocyanates (so-calledsemi-prepolymers) may be employed in the prepolymer technique. Theorganic polyisocyanate may be any organic polyisocyanate describedpreviously.

Polyester polyols containing modification by fatty acids, (commonlyreferred to as alkyd polyols) which optionally may be used in thepreparation of the isocyanate-terminated prepolymer, are generallyknown. As used herein, the term "alkyd polyols" refers to alkyd resinscontaining hydroxyl functionality. They typically are produced byreacting polyhydric alcohols, polycarboxylic acids, and fatty acidsderived from drying, semi-drying or non-drying oils in variousproportions depending upon the extent of hydroxyl functionality andproperties desired in the alkyd polyol. The techniques of preparingalkyd resins are well known generally. Usually, the process involvesreacting together the polycarboxylic acid and fatty acid or a partialglyceride thereof and the polyhydric alcohol (the latter usually isstoichiometric excess) in the presence of a catalyst such as litharge,sulfuric acid, or sulfonic acid to effect esterification with evolutionof water. Examples of polyhydric alcohols typically used for preparationof the alkyd polyols include the simple diols, triols and higher hydricalcohols known in the art including but not limited to the previouslydescribed simple diols, triols and higher hydric alcohols. Examples ofpolycarboxylic acids suitable for preparation of the alkyd polyolsinclude those set forth previously in the description of polycarboxylicacids useful for preparing the polyester polyols in general. Examples ofsuitable fatty acids include saturated and unsaturated acids such asstearic acid, oleic acid, ricinoleic acid, palmitic acid, linoleic acid,linolenic acid, licanic acid, elaeostearic acid, clupanodonic acid andmixtures thereof. The fatty acids may be in the form of the free acidswith sufficient excess of the polyhydric alcohol being incorporated intothe esterification mixture to compensate for their inclusion. However,in many instances, it is preferred to employ glyceride oils which havebeen partially alcoholized with a sufficient amount of a polyhydricalcohol such as glycerol to supply the requisite amount of availablehydroxyls for the formation of the alkyd polyol.

The divalent radical represented by X in formula (I) above can beprovided from a compound containing at least 2 carbon atoms, at least 1functional group reactive with a moiety on the silicon-containingcompound, and at least one amino group. Optionally, the divalent radicalrepresented by X in formula (I) can be provided from a compound asdescribed above but additionally containing one or more groups selectedfrom ether, amino, amido, carbamate, urea, and thio.

Typically, compounds which have been utilized herein to provide thedivalent radical X in formula (I) include hydroxyl-containing aminessuch as alkanolamines, dialkanolamines, alkyl alkanolamines, and arylalkanolamines containing at least 2 and typically no more than 18 carbonatoms in the alkanol, alkyl and aryl chains. Examples of suchhydroxyl-containing amines include: ethanolamine, propanolamine,2-amino-2-methyl propanol, N-methylethanolamine, diethanolamine,N-phenylethanolamine, N-cyclohexylethanolamine,N-(3-ethylthio-2-hydroxypropyl) ethylenediamine,N-(3-ethylthio-2-hydroxypropyl)ethylamine,N-(3-butylthio-2-hydroxypropyl)ethylenediamine,N-(4-cyclohexylthio-3-hydroxybutyl)ethylenediamine,N-(3-allylthio-2-hydroxypropyl)hexamethylenediamine,N-(2-hydroxypropyl)ethylenediamine, N-(2-hydroxyethyl)ethylenediamine,para-aminophenol, aminoethylethanolamine,monohydroxyethyldiethylenetriamine, bishydroxyethyl-diethylenetriamine,and 2-amino-1-phenylethanol.

A wide variety of hydroxyl-containing amines can be prepared, forexample, in known manner by reacting monoamines or polyamines with amonoepoxide provided that the amine reactant contains at least oneprimary amino group. Examples of the monoamines and polyamines include:methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,tert-butylamine, n-hexylamine, cyclohexylamine, benzylamine,ethylenediamine, diethylenetriamine, triethylenetetramine,1,4-diaminobutane, and hexamethylene-diamine. Examples of themonoepoxides include: ethylene oxide, propylene oxide, styrene oxide,cyclohexene oxide, phenyl glycidyl ether, allyl glycidyl ether, tolylglycidyl ether, the diacetate of a monoglycidyl ether of glycerol; thedipropionate of a monoglycidyl ether of glycerol and epichlorohydrin.The reaction between the amines and monoepoxides is usually effectedmerely by brining the components together in proper proportions.

Hydroxyl-containing amines which also contain amide groups can beprepared, for example, in known manner by reacting polyamines, such asthose described previously for reaction with monoepoxides, with lactonessuch as caprolactone, propylolactone and methyl caprolactone.Hydroxyl-containing amines which also contain amide and urea groups canbe prepared, for example, in known manner by reacting a polyisocyanateor isocyanate-terminated prepolymer, such as those described previously,with an excess of polyamine to form the urea-containing polyamineproduct and subsequently reacting this product with a lactone to producethe hydroxyl-containing amine which also contains amide and urea groups.Hydroxyl-containing amines which also contain carbamate (i.e. urethane)groups can be prepared, for example, in known manner by reactingpolyamines such as those described previously with alkylene carbonatessuch as propylene carbonate to produce the hydroxyl-containing amineswhich also contain a carbamate (i.e. urethane) group. An example ofanother known way of producing hydroxyl-containing amines which alsocontain carbamate groups is to react a polyisocyanate orisocyanate-terminated prepolymer with an excess of polyamine to form theurea-containing polyamine product and subsequently to react this productwith an alkylene carbonate such as propylene carbonate to produce thehydroxyl-containing amine which also contains urea groups can beprepared in known manner by reacting together a polyamine, ahydroxyl-functional amine such as an alkanolamine, etc., and apolyisocyanate or isocyanate-terminated prepolymer. The aforesaidhydroxyl-containing amines are merely illustrative of varioushydroxyl-containing amines which are examples of suitable startingmaterials for providing the divalent radical X in formula (I) forpreparing a resin of the invention by reaction of thehydroxyl-containing amine with the organic isocyanate having an averagefunctionality of at least one and a silicon-containing compoundcorresponding to the following formula (III) ##STR6## wherein R²independently represents hydrogen, a C₁ to C₁₀ alkyl group, a C₄ to C₁₀cycloalkyl group, a C₆ to C₁₀ aryl group, or a monovalent aminoalkylgroup, that is directly attached to Si,

Y independently represents a hydrolyzable group that is attacheddirectly to Si,

m is an integer ranging from 1 to 5,

e is a positive integer wherein 1≦e≦12,

d is a zero or a positive integer wherein 0≦d≦10, and 4≦d+e≦12, and

wherein x is a positive number which is equal to or less than theaverage isocyanate functionality of said organic isocyanate.

A silicon-containing compound for preparing a resin of the invention isorganic and is essentially free of alkali metal ions which distinguishesit from known inorganic silicates such as alkali metal silicatesincluding, for example, sodium orthosilicate. Additionally, thesilicon-containing compound has groups directly bonded to silicon whichare hydrolyzable. Examples of the hydrolyzable groups include ##STR7##and the C₂ to C₃ residue of a 1,2- or 1,3- glycol wherein R³, R⁴, R⁵, R⁶and R⁷ are as set forth previously in the examples for Y under thedefinitions for formula (II).

Silicon-containing compounds corresponding to formula (III) may bymonosilicon-containing and/or polysilicon-containing materials. Examplesof monosilicon-containing compounds include compounds such astetraethylorthosilicate, methyltriethoxysilane, dimethyldimethoxysilane,etc. Examples of polysilicon-containing compounds includehexaethoxydisiloxane, dimethyltetraethoxydisiloxane,octaethoxytrisiloxane, methyl-pentaethoxydisiloxane, as well ascompounds containing a plurality of repeating siloxane linkages (i.e., aplurality of ##STR8## linkages). Typically the polysilicon-containingcompounds are prepared in generally known manner by the hydrolysis andcondensation of monomeric silicon-containing compounds containingsilicon atoms attached to substituents convertible to silanol ##STR9##groups. These hydrolysis reactions typically may be illustrated as,

    Si(X).sub.4 +H.sub.2 O=(X).sub.3 SiOH+HX,

in which X can be an easily hydrolyzable group such as C₁ -C₃ alkoxy,##STR10## which are defined as above. The silanol-containing productsare condensed to produce ##STR11## linkages in the silicon-containingcompounds. Of course, it should be understood that polymericsilicon-containing compounds include those hydrolyzed and condensedmaterials prepared from precursors which contain silicon atoms attachedto hydrolyzable substituents other than the hydrolyzable groups setforth above, such hydrolyzable substituents including, for example,hydrogen.

It is also considered to be within the scope of the present invention touse mixtures of monosilicon-containing compounds andpolysilicon-containing compounds to prepare a resin of the presentinvention.

By way of illustration, an especially desirable class ofmonosilicon-containing compounds suitable for preparing resins of theinvention include organosilicates. Examples of organosilicates include:tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane,methoxytriethoxysilane, and the like.

In a procedure for preparing a resin of the invention, an amino-alcoholsuch as 2-amino-2-methylpropanol is first reacted with an organosilicatesuch as tetraethylorthosilicate to produce a product containingaminoalkyloxy and ethoxysilyl groups, which product can be referred toas an aminoalkyloxy silane. During the reaction of the aminoalcohol andthe organosilicate, the ethoxysilyl group of the organosilicate reactswith the hydroxyl group of the aminoalcohol to produce an aminoalkyloxysilane. Thereafter, the aminoalkyloxy silane is reacted with anisocyanate-terminated polyisocyanate prepolymer to produce an ungelledresin of the invention which, preferably, is essentially free ofisocyanate groups. The above procedure is considered to be merelyillustrative of a preferred way to produce a resin of the invention. Thefollowing is an illustrative description of additional ways by whichresins of the invention can be prepared.

In one procedure for preparing a resin of the invention an excess of apolyamine such as those described previously is reacted with apolyisocyanate or isocyanate-terminated prepolymer to form anamine-terminated product which also contains urea groups. Thereafter,the amine-terminated product is reacted with an alkylene carbonate suchas propylene carbonate to form a hydroxyl-functional product which alsocontains urea and urethane groups. Thereafter, the hydroxyl-functionalproduct is reacted with the silicon-containing compound corresponding toformula (III) to form a resin of the invention.

In another procedure for preparing a resin of the invention a polyaminesuch as those described previously, a hydroxyl-containing amine such asthose described previously, and a polyisocyanate orisocyanate-terminated prepolymer are reacted in relative proportionssuch that a hydroxyl-functional product which also contains urea groupsis obtained which thereafter is reacted with a silicon-containingcompound corresponding to empirical formula (III) to form a resin of theinvention.

In another procedure for preparing a resin of the invention apolyisocyanate or isocyanate-terminated prepolymer is reacted with anexcess of a hydroxyl-containing amine such as those described previouslyto form a first hydroxyl-functional product containing urea groups.Thereafter, this first hydroxyl-functional product (optionally afterreaction with a silicon-containing compound corresponding to formula IIIabove) is reacted at elevated temperature with an alkylene oxide such asethylene oxide, propylene oxide and the like; or a monoglycidyl ethersuch as butyl glycidyl ether, phenyl glycidyl ether and the like; orwith a monoglycidyl ester such as the glycidyl ester of versatic acidavailable as CARDURA-E (from Shell Chemical Co.) and the like to form asecond hydroxyl-functional product containing urea as well as ethergroups. Thereafter, this second hydroxyl-functional product is reactedwith a silicon-containing compound corresponding to empirical formula(II) to form a resin of the invention.

In another procedure for preparing a resin of the invention apolyisocyanate or isocyanate-terminated prepolymer is reacted with anexcess of a hydroxyl-containing amine such as those described previouslyto form a first hydroxyl-functional product containing urea groups.Thereafter, this first hydroxyl-functional product is reacted with alactone such as caprolactone, propylolactone, butyrolactone andmethylcaprolactone to form a second hydroxyl-functional productcontaining urea as well as ester groups. Thereafter, this secondhydroxyl-functional product is reacted with a silicon-containingcompound corresponding to formula (III) to form a resin of theinvention.

It is preferred that a resin of the invention be essentially free ofisocyanate radicals.

As can be appreciated from the disclosure and examples herein, a productresin of the invention typically will contain a mixture of compounds.For example, when a resin of the invention is prepared by reacting anisocyanate-functional prepolymer and an aminoalkyloxy silane (e.g., fromthe reaction of an amino alcohol and a silicon-containing compoundcorresponding to formula III) the resultant distribution of compounds inthe product mixture will be determined at least in part by thestatistics of reaction involved in either or both of (1) the reactionsleading to formation of the isocyanate-functional prepolymer and (2) thereactions leading to formation of the aminoalkyloxy silane, as well asthe reaction involved between the isocyanate-functional prepolymer andthe aminoalkyloxy silane. However, one or more compounds correspondingto formula (I) will be present in a resin of the invention.

A coating composition of the invention comprises a resin of theinvention either as the sole film-forming resin or optionally incombination with other compatible resins known for use in coatingcompositions. Examples of such other resins which may be employed incombination with a resin of the invention in a coating compositioninclude the generally known cellulosics, acrylics, aminoplasts,urethanes, polyesters, polyethers, epoxies and mixtures thereof.

Cellulosics refer to the generally known thermoplastic polymers whichare derivatives of cellulose, examples of which include: nitrocellulose;organic esters and mixed esters of cellulose such as cellulose acetate,cellulose propionate, cellulose butyrate, and preferably celluloseacetate butyrate (CAB); and organic ethers of cellulose such as ethylcellulose.

Acrylic resins refer to the generally known addition polymers andcopolymers of acrylic and methacrylic acid and their ester derivatives,acrylamide and methacrylamide, and acrylonitrile and methacrylonitrile.Additional examples of acrylic monomers which can be additionpolymerized to form acrylic resins which may be used in compositions ofthe invention include methyl acrylate, ethyl acrylate, isopropylacrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate,cyclohexyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, methylmethacrylate, ethyl methacrylate, isopropyl methacrylate, butylmethacrylate, t-butyl methacrylate, n-hexyl methacrylate, decylmethacrylate, isodecyl methacrylate, lauryl methacrylate stearylmethacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornylmethacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate,glycidyl methacrylate, dimethylaminoethyl methacrylate, andt-butylaminoethyl methacrylate. Moreover, where desired, various otherunsaturated monomers can be employed in the preparation of acrylicresins for compositions of the invention examples of which include:vinyl aromatic hydrocarbons such as styrene, alpha methyl styrene, andvinyl toluene; vinyl acetate; vinyl chloride; and unsaturatedsilicon-containing monomers such as gamma-methacryloxypropyltriethoxysilane, gamma-acryloxypropyl triethoxysilane, and the like.

Aminoplast resins refer to the generally known condensation products ofan aldehyde with an amino- or amido-group containing substance examplesof which include the reaction products of formaldehyde, acetaldehyde,crotonaldehyde, benzaldehyde and mixtures thereof with urea, melamine,or benzoguanamine. Preferred aminoplast resins include the etherifiedproducts obtained from the reaction of alcohols and formaldehyde withurea, melamine, or benzoguanamine. Examples of suitable alcohols forpreparing these etherified products include: methanol, ethanol,propanol, butanol, hexanol, benzylalcohol, cyclohexanol,3-chloropropanol, and ethoxyethanol.

Urethane resins refer to the generally known thermosetting orthermoplastic urethane resins prepared from organic polyisocyanates andorganic compounds containing active hydrogen atoms as found for examplein hydroxyl, and amino moieties. Some examples of urethane resinstypically utilized in one-pack coating compositions include: theisocyanate-modified alkyd resins sometimes referred to as "uralkyds";the isocyanate-modified drying oils commonly referred to as "urethaneoils" which cure with a drier in the presence of oxygen in air; andisocyanate-terminated prepolymers typically prepared from an excess ofone or more organic polyisocyanates and one or more polyols including,for example, simple diols, triols and higher alcohols, polyester polyolsand polyether polyols. Some examples of systems based on urethane resinstypically utilized as two-pack coating compositions include an organicpolyisocyanate or isocyanate-terminated prepolymer (first pack) incombination with a substance (second pack) containing active hydrogen asin hydroxyl or amino groups along with a catalyst (e.g., an organotinsalt such as dibutyltin dilaurate or an organic amine such astriethylamine or 1,4-diazobicyclo-(2:2:2)octane). The activehydrogen-containing substance in the second pack typically is apolyester polyol, a polyether polyol or an acrylic polyol known for usein such two-pack urethane resin systems. Many coating compositions basedon urethanes (and their preparation) are described extensively inChapter X Coatings, pages 453-607 of Polyurethanes: Chemistry andTechnology, Part II by H. Saunders and K. C. Frisch, IntersciencePublishers (N.Y., 1964).

Polyester resins are generally known and are prepared by conventionaltechniques utilizing polyhydric alcohols and polycarboxylic acids.Examples of suitable polyhydric alcohols include: ethylene glycol;propylene glycol; diethylene glycol; dipropylene glycol; butyleneglycol; glycerol; trimethylolpropane; pentaerythritol; sorbitol;1,6-hexanediol; 1,4-cyclohexanediol; 1,4-cyclohexanedimethanol;1,2-bis(hydroxyethyl)cyclohexane; and2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate. Examplesof suitable polycarboxylic acids include: phthalic acid, isophthalicacid, terephthalic acid; trimellitic acid; tetrahydrophthalic acid,tetrachlorophthalic acid; adipic acid; azelaic acid; sebacic acid,succinic acid, maleic acid; glutaric acid; malonic acid; pimelic acid;suberic acid; 2,2-dimethylsuccinic acid; 3,3-dimethylglutaric acid;2,2-dimethylglutaric acid; maleic acid; fumaric acid; and itaconic acid.Anhydrides of the above acids, where they exist, can also be employedand are encompassed by the term "polycarboxylic acid". In addition,certain substances which react in a manner similar to acids to formpolyesters are also useful. Such substances include lactones such ascaprolactone, propylolactone and methyl caprolactone, and hydroxy acidssuch as hydroxy caproic acid and dimethylolpropionic acid. If a triol orhigher hydric alcohol is used, a monocarboxylic acid, such as aceticacid and benzoic acid may be used in the preparation of the polyesterresin. Moreover, polyesters which may be used in compositions of theinvention are intended to include polyesters modified with fatty acidsor glyceride oils of fatty acids (i.e., conventional alkyd resins).Alkyd resins typically are produced by reacting the polyhydric alcohols,polycarboxylic acids, and fatty acids derived from drying, semi-drying,and non-drying oils in various proportions in the presence of a catalystsuch a litharge, sulfuric acid, or a sulfonic acid to effectesterification. Examples of suitable fatty acids include saturated andunsaturated acids such as stearic acid, oleic acid, ricinoleic acid,palmitic acid, linoleic acid, linolenic acid, licanic acid, elaeostearicacid, and clupanodonic acid.

Polyether resins are generally known and are prepared by well knowntechniques. Examples of polyethers include the poly(oxyalkylene) glycolsprepared by the acid or base catalyzed addition of an alkylene oxidesuch as ethylene oxide and/or propylene oxide to initiator compoundssuch as ethylene glycol, propylene glycol, diethylene glycol,dipropylene glycol, trimethylolpropane, glycerol, penterythritol,sorbitol, sucrose and the like. Additional examples of polyethersinclude the generally known poly(oxytetramethylene) glycols prepared bythe polymerization of tetrahydrofuran in the presence of Lewis acidcatalysts such as boron trifluoride, tin (IV) chloride, antimonypentachloride, antimony trichloride, phosphorous pentafluoride, andsulfonyl chloride. Other examples of polyethers include the generallyknown reaction products of 1,2-epoxide-containing compounds with polyolssuch as simple diols, triols and higher hydric alcohols known in the artsuch as those described previously herein as useful in the preparationof isocyanate-terminated prepolymers.

Epoxy resins, often referred to simply as "epoxies", are generally knownand refer to compounds or mixtures of compounds containing more than one1,2-epoxy group of the formula ##STR12## i.e., polyepoxides. Thepolyepoxides may be saturated or unsaturated, aliphatic, cycloaliphatic,aromatic or heterocyclic. Examples of suitable polyepoxides include thegenerally known polyglycidyl ethers of polyphenols and/or polyepoxideswhich are acrylic resins containing pendant and/or terminal 1,2-epoxygroups. Polyglycidyl ethers of polyphenols may be prepared, for example,by etherification of a polyphenol with epichlorohydrin or dichlorohydrinin the presence of an alkali. Examples of suitable polyphenols include:1,1-bis(4-hydroxyphenyl)ethane; 2,2-bis(4-hydroxyphenyl)propane;1,1-bis(4-hydroxyphenyl)isobutane;2,2-bis(4-hydroxytertiarybutylphenyl)propane;bis(2-hydroxynaphthyl)methane; 1,5-dihydroxynaphthalene;1,1-bis(4-hydroxy-3-allylphenyl)ethane; and the hydrogenated derivativesthereof. The polyglycidyl ethers of polyphenols of various molecularweights may be produced, for examples, by varying the mole ratio ofepichlorohydrin to polyphenol in known manner.

Epoxy resins also include the polyglycidyl ethers of mononuclearpolyhydric phenols such as the polyglycidyl ethers of resorcinol,pyrogallol, hydroquinone, and pyrocatechol.

Epoxy resins also include the polyglycidyl ethers of polyhydric alcoholssuch as the reaction products of epichlorohydrin or dichlorohydrin withaliphatic and cycloaliphatic compounds containing from two to fourhydroxyl groups including, for example, ethylene glycol, diethyleneglycol, triethylene glycol, dipropylene glycol, tripropylene glycol,propane diols, butane diols, pentane diols, glycerol, 1,2,6-hexanetriol,pentaerythritol, and 2,2-bis(4-hydroxycyclohexyl)propane.

Epoxy resins additionally include polyglycidyl esters of polycarboxylicacids such as the generally known polyglycidyl esters of adipic acid,phthalic acid, and the like.

Addition polymerized resins containing epoxy groups may also beemployed. These polyepoxides may be produced by the additionpolymerization of epoxy functional monomers such as glycidyl acrylate,glycidyl methacrylate and allyl glycidyl ether optionally in combinationwith ethylenically unsaturated monomers such as styrene, alpha-methylstyrene, alpha-ethyl styrene, vinyl toluene, t-butyl styrene,acrylamide, methacrylamide, acrylonitrile, methacrylonitrile,ethacrylonitrile, ethyl methacrylate, methyl methacrylate, isopropylmethacrylate, isobutyl methacrylate, and isobornyl methacrylate.

Many additional examples of epoxy resins are described in the Handbookof Epoxy Resins, Henry Lee and Kris Neville, 1967, McGraw Hill BookCompany.

The resins of the invention can also be combined with various polyols toform compositions of the invention. Examples of polyols which may beutilized in compositions of the invention include the polyols in thebroad classes previously described with respect to polyols suitable forpreparation of the isocyanate-terminated prepolymers, namely: simplediols, triols, and higher hydric alcohols; polyester polyols optionallymodified with a fatty acid; polyether polyols; amide-containing polyols;and polyurethane polyols.

In addition to the foregoing components, the compositions of thisinvention may contain optional ingredients, including various pigmentsof the type ordinarily utilized in coatings of this general class. Inaddition, various fillers; plasticizers, antioxidants; mildewcides andfungicides; surfactants; various flow control agents including, forexample, thixotropes and additives for sag resistance and/or pigmentorientation based on polymer microparticles (sometimes referred to asmicrogels) described, for example, in U.S. Pat. Nos. 4,025,474;4,055,607; 4,075,141, 4,115,472; 4,147,688; 4,180,489; 4,242,384;4,268,547; 4,220,679; and 4,290,932 the disclosures of which are herebyincorporated by reference; and other such formulating additives may beemployed in some instances.

The compositions herein can be applied by any conventional method,including brushing, dipping, flow coating, roll coating, etc., but theyare most often applied by spraying. The compositions may be applied overa wide variety of substrates such as wood, metals, glass, cloth,plastics, foams and the like, as well as over primers.

Pigments suitable for a composition of the invention include a widevariety of pigments generally known for use in coating compositions.Suitable pigments include both metallic-flake pigments and various whiteand colored pigments.

Examples of metallic-flake pigments include the conventional metallicflakes such as aluminum flakes, nickel flakes, tin flakes, silverflakes, chromium flakes, stainless steel flakes, gold flakes, copperflakes and combinations thereof. Of the metallic-flake pigments,nonleafing aluminum flakes are preferred.

Examples of white and colored pigments include generally known pigmentsbased on metal oxides; metal hydroxides; metal sulfides; metal sulfates;metal carbonates; carbon black; china clay; phthalo blues and greens,organo reds, and other organic dyes.

Coating compositions of the invention based on the resins of theinvention can provide cured films having an excellent combination ofproperties such as the hardness required for automotive coatings bothfor original equipment automotive applications and automotiverefinishing applications, good solvent and water resistance, highinitial gloss, good impact resistance and excellent long term durabilitywhen exposed to weathering conditions as exist, for example, in Florida,United States of America.

Typically, a composition of the invention comprises a resin of theinvention, a cure-promoting catalyst, and when desired, a solvent.

Examples of cure-promoting catalysts which may be employed in acomposition of the invention include: acids and acid salts such asp-toluenesulfonic acid, butylstannoic acid, n-butylphosphoric acid,triflic acid (i.e., trifluoromethane sulfonic acid), diethylammoniumtriflate, tin naphthenate, tin benzoate, tin octoate, tin butyrate,dibutyltin dilaurate, dibutyltin diacetate, iron stearate, and leadoctoate; titanates such as tetraisopropyl titanate and tetrabutyltitanate; oxides such as dibutyltin oxide; and bases such as isophoronediamine, methylene dianiline, imidazole, aminopropyltriethoxysilane,aminoalcohols and others basic nitrogen-containing compounds. Thepreferred cure-promoting catalyst is diethylammonium triflate. A patentapplication Ser. No. 683,737 filed Dec. 19, 1984 titled CATALYSTS FORCURABLE COATING VEHICLE BASED UPON AMINOALKYLOXY SILANES AND ORGANICISOCYANATES in the name of P. Prucnal is directed to compositionsdescribed herein containing a catalyst selected from triflic acid (i.e.,trifluoromethane sulfonic acid), a neutralization product of triflicacid with ammonia, a neutralization product of triflic acid with anamine, a tetraalkyl ammonium salt of triflic acid, and mixtures thereof.

The specific amounts of cure-promoting catalyst which can be included inthe compositions of the invention may vary considerably depending uponfactors such as curing temperature, rate of cure desired, optionalfilm-forming resins in the compositions in addition to a resin of theinvention, the amount of moisture present in the ambient atmosphere, andthe like. However, in general, a coating composition of the inventionmay contain from about 0.1 parts to about 5 parts or more by weight ofcure-promoting catalyst based on 100 parts by weight of resin solids inthe composition.

Although it is preferred to minimize the content of organic solvent incompositions of the invention, where desired, generally known organicsolvents may be included since the resins of the invention generally arecompatible with organic solvents. Examples of suitable solvents include:alcohols, such as methanol, ethanol, propanol, butanol and the like; themono- and dialkyl ethers of ethylene and propylene glycol such asethylene glycol monoethyl ether, ethylene glycol monobutyl ether,ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate,ethylene glycol monohexyl ether acetate, propylene glycol monoethylether and propylene glycol dibutyl ether; the mono- and dialkyl ethersof diethylene glycol such as diethylene glycol monoethyl ether,diethylene glycol dibutyl ether, diethylene glycol diethyl ether anddiethylene glycol monobutyl ether acetate; ketones such as methylethylketone; esters such as butyl-acetate; hydrocarbons such as xylene andtoluene; N-methyl-2-pyrrolidone; dimethyl formamide; and mixturesthereof.

Coating compositions of the invention comprising a resin of theinvention typically can be cured by heating in the presence ofatmospheric moisture; although, where curing time is not an importantconsideration, they may be cured at ambient temperature. Thus, once aresin of the invention and cure-promoting catalyst are brought incontact with each other, as by admixing, and exposed to the ambientatmosphere, the composition will begin to cure. Accordingly, it isdesirable in some instances to prepare a composition of the invention inthe form of a two-package system, i.e., one package containing a resinof the invention along with desired optional ingredients and a secondpackage containing the cure-promoting catalyst. When it is desired tocoat a substrate with the composition, the components of the twopackages are merely mixed together just prior to application and theresulting composition applied to the substrate by any of the methodsdescribed above.

As indicated previously, a coating composition of the invention cancomprise a resin of the invention as the sole film-forming resin in thecomposition. In coating compositions of the invention containing a resinof the invention, a cure-promoting catalyst, and various optionalingredients including, for example, those ingredients describedpreviously such as other film-forming resins and polyols, the amounts ofthe individual components may vary widely depending on the intended useof the composition. However, generally coating compositions of theinvention comprise from about 100 to about 10 percent by weight of resinof the invention, and from about 0 to about 90 percent by weight ofoptional other film-forming resin and/or polyol, based on the totalweight of the composition. Preferred coating compositions of theinvention comprise from about 30 to 100 percent by weight of resin ofthe invention and 70 to 0 percent by weight of optional otherfilm-formin resin and/or polyol, based on the total weight of thecomposition. In the compositions of the invention where the percent byweight of resin of the invention, optional other resins as describedpreviously, optional polyol, and cure-promoting catalyst based on thetotal weight of the composition do not add up to 100 percent by weight,the balance is comprised of other optional ingredients of the typesdescribed previously.

The following examples illustrate the invention. Amounts and percentagesare by weight unless specified otherwise. When used herein "pbw" means"parts by weight." Tests referred to in the following examples areconducted as follows.

TESTS

(1) Gloss 60°--The value for gloss 60° represents the percent specularreflectance of light from the surface of the coating at an angle of 60degrees from the direction normal to the surface of the coating.

(2) Hardness--An EAGLE Turquoise Drawing Pencil (from BEROL Corporation)is sharpened and the point is sanded to provide a flattened surface. Theflattened tip is scraped at about a 45° angle to the coating whilestrong downward pressure is applied to the pencil. The value forhardness represents the designation of the "lead" in the hardest EAGLETurquoise Drawing Pencil which does not scratch the coating in thistest.

(3) Solvent Rubs--The number of double rubs is understood to mean thenumber of back and forth finger rubs across the coating with a clothdipped in the indicated solvent. The number of double rubs indicated isthe number that the cured coating can withstand before the substratebecomes visible through the coating. However, when the term "passed" isused to describe the results of this test, it means that the coatingwithstands at least 50 solvent rubs with the indicated solvent.

(4) Acid Resistance--To a coated substrate is applied a spot formed from10 drops of 10 percent by volume muriatic acid (37 percent commercialgrade hydrochloric acid) in tap water. The spot is covered with a watchglass and allowed to remain on the coating for 15 minutes at roomtemperature. Thereafter the spot of acid is washed off under running tapwater. The term "passed" means that the coating shows no visibleevidence of deterioration when subjected to this test.

(5) Watersoak--The coating on a substrate is scored down to thesubstrate in a crosshatched pattern of 1/16×1/16 inch squares.Thereafter, the substrate is immersed in deionized water at 100° F.(37.8° C.) for 24 hours, removed, and wiped dry. Next, tape (3MTransparent No. 710, 3/4 inch wide) is firmly applied to thecrosshatched area so as to eliminate voids and air pockets andthereafter sharply ripped from the coating. The term "passed" means thatthe crosshatched area is not removed from the substrate.

(6) Detergent Resistance--A coated substrate is soaked for 72 hours at100° F. (37.8° C.) in a 15 gallon (56.8 liter) tank containing 505 grams(g) of sodium tetrapyrophosphate decahydrate, 107.7 g of anhydroussodium sulfate, 39.7 g of sodium metasilicate, 5.7 g of anhydrous sodiumcarbonate, and 113.4 g of a sodium alkylarylsulfonate available asFisher S-198 from Fisher Scientific Co. The term "passed" means that thecoating shows no visible evidence of deterioration when subjected tothis test.

(7) Impact--A coating on a substrate is subjected to a falling weightimpact substantially according to test ASTM D 2794-69 (1974). Resultsare reported in the form "x/y" wherein x represents inch-pounds impactedon the coated side of the panel and y represents inch-pounds impacted onthe reverse side.

(8) Stripper Resistance--A phenolic based paint stripper (EPCO 803 fromEnsign Products Company) is applied directly to the coating, allowed toremain on the coating for 4 minutes, and thereafter removed by means ofrunning water. The term "passed" means that the coating shows no visibleevidence of deterioration and the coating remains adhered to thesubstrate.

(9) Mortar Resistance--Mortar in the form of a soft paste prepared bymixing 75 g of building lime (ASTM C 207-74) and 225 g of dry sand, bothpassing 10-mesh wire screen with about 100 g water, is applied at athickness of about 1/4 inch to the coating on a substrate. Thereafterthe coated substrate is exposed for 24 hours to 100 percent relativehumidity at 100° F. (37.8° C.). The term "passed" means that after the24 hour period the mortar dislodges easily from the coating without lossof coating adhesion and without visible evidence of deterioration of thecoating.

(10) Solids Content--The solids contents of compositions herein aredetermined by generally known procedures either at 105° C. for 2 hoursor 150° C. for 2 hours.

EXAMPLE 1

(a) An aminoalkyloxy silane is prepared as follows. A reaction vesselequipped with heating mantle, thermometer, stirrer and distillationcolumn is charged at room temperature with a reaction mixture of 359.6grams of 2-amino-2-methylpropanol and 840.4 grams of tetraethylorthosilicate. The reaction mixture is heated and distillate iscollected according to the schedule set forth in the following TABLE 1.The temperature of the reaction vessel and the head temperature of thedistillation column are given for the end of each corresponding timeperiod. The amount of distillate as represented in each horizontal rowrepresents the total distillate collected up to the end of thecorresponding time period (i.e., including that collected during thepreceding time periods). The resulting product is an aminoalkyloxysilane.

                  TABLE 1                                                         ______________________________________                                                 Temperature of                                                                            Head                                                              Reaction    Temperature Total Distillate                             Time (min)                                                                             Vessel (°C.)                                                                       (°C.)                                                                              Collected (ml)                               ______________________________________                                         0-50    112         79           20                                          50-80    120         78          125                                           80-140  145         80          200                                          140-182  172         71          235                                          ______________________________________                                    

(b) A polyisocyanate polymer is prepared as follows. A reaction vesselequipped with heating mantle, thermometer, stirrer, reflux condenser andsource of nitrogen is charged at room temperature under a blanket ofnitrogen with 77.3 grams of dimethylolpropionic acid, 815 grams ofPCP-0200¹, 1108 grams of DESMODUR-W², and 220 grams of methylisobutylketone. The reaction mixture is heated over a period of 114 minutes to atemperature of 115° C. after which the reaction mixture is allowed tocool over a period of 19 minutes to a temperature of 94° C. Thereafter,the reaction mixture is maintained at a temperature of 94° C. for anadditional 107 minutes. The resulting product is a polyisocyanateprepolymer having an isocyanate equivalent weight of 579 and an acidvalue of 14.6.

(c) The aminoalkyloxy silane of part (a) immediately above in an amountof 520.6 grams is mixed at room temperature with 740 grams of anhydrousethanol. To the resultant mixture is slowly added 1200 grams of thepolyisocyanate prepolymer of part (b) immediately above while thetemperature is maintained at less than 55° C. The resulting resincomposition has an acid value of 7.8, contains 0.01 milliequivalents ofamine per gram, has a Gardner-Holdt bubble tube viscosity of 10.2seconds, a solids content at 105° C. of 60.0 percent by weight, and asolids content at 150° C. of 54.7 percent by weight.

The following EXAMPLE 2 describes a coating composition prepared fromthe polyisocyanate prepolymer of EXAMPLE 1.

EXAMPLE 2

(a) A vehicle is prepared containing 89.6% by weight of the resincomposition of EXAMPLE 1(c) immediately above, 10.0% by weight of analiphatic diepoxide¹ and 0.4% by weight of diethylammonium triflate.

A coating composition is prepared by sand milling carbon black, red ironoxide, yellow iron oxide and titanium dioxide with a portion of thevehicle to prepare a pigment paste. The pigment paste is let down withan additional portion of the vehicle to provide a coating compositioncontaining 1.76 g carbon black, 4.55 g yellow iron oxide, 2.35 g rediron oxide and 4.55 g titanium dioxide for each 100 g of vehicle solids.

(b) Aluminum panels (24 gauge; ALODINE 407-47 pretreatment) are coatedwith the coating composition of part (a) immediately above. The coatingson the panels are cured to a dry film thickness of about 1 mil at thetemperatures and for the lengths of time set forth in the followingTABLE 2. Tests (1) through (9) as described infra are performed on thecured panels. The results of these tests are summarized in TABLE 2.

                  TABLE 2                                                         ______________________________________                                        Curing Time (min)/                                                                         10'/325° F.,                                                                     15'/325° F.,                                                                      10'/350° F.,                         Temperature  163° C.                                                                          163° C.                                                                           177° C.                              ______________________________________                                        Gloss 60°                                                                           95        96         95                                          Hardness     H         3H         3H                                          Solvent Rubs Marginal  Pass       Pass                                        (Methylethyl ketone)                                                          Acid Resistance                                                                            Pass      Pass       Pass                                        Watersoak    Fail      Pass       Pass                                        Detergent Resistance                                                                       Fail      Pass       Pass                                        Direct Impact                                                                              40/<20    >60/>60    >60/>60                                     Stripper Resistance                                                                        Fail      Pass       Pass                                        Mortar Resistance                                                                          Fail      Pass       Pass                                        ______________________________________                                         .sup.1 A diglycidylether of hydrogenated bisphenolA (DRH 151.1 from Shell     Chemical Company.)                                                       

Additionally, cured panels prepared as described immediately above,after outdoor exposure in Florida, U.S.A. for at least 14 months showvery good durability.

EXAMPLE 3

(a) An aminoalkyloxy silane is prepared as follows. A reaction vesselequipped with heating mantle, thermometer, stirrer and distillationcolumn is charged at room temperature with a reaction mixture of 1000grams of 2-amino-2-methylpropanol and 2337 grams oftetraethylorthosilicate. The reaction mixture is heated and distillateis collected according to the schedule set forth in the following TABLE3. The temperature of the reaction vessel and the head temperature ofthe distillation column are given for the end of each corresponding timeperiod. The amount of distillate as represented in each horizontal rowrepresents the total distillate collected up to the end of thecorresponding time period (i.e., including that collected during thepreceding time period). The resulting product is an aminoalkyloxy silaneand has a theoretical amine equivalent weight of 251.

                  TABLE 3                                                         ______________________________________                                                 Temperature of                                                                            Head                                                              Reaction Vessel                                                                           Temperature Total Distillate                             Time (min)                                                                             (°C.)                                                                              (°C.)                                                                              Collected (ml)                               ______________________________________                                         0-70    112         79          100                                           70-170  120         78          325                                          170-270  120         78          435                                           0-95    142         78          490                                           95-140  159         75          560                                          140-220  175         74          650                                          220-260  185         73          675                                          260-290  190         69          680                                          290-315  192         65          680                                          315-330  190         61          680                                          ______________________________________                                         *Heating is discontinued and the reaction mixture allowed to cool.       

(b) A polyisocyanate prepolymer is prepared as follows. A reactionvessel equipped with heating mantle, thermometer, stirrer, refluxcondenser, and source of nitrogen is charged at room temperature under ablanket of nitrogen with 139.3 g of dimethylol propionic acid, 1468.4 gof PCP-0200¹, 1996.1 g of DESMODUR-W², and 396.3 g of methylisobutylketone. The reaction mixture is heated over a period of 185 minutes to atemperature of 103° C. after which the reaction mixture is allowed tocool to room temperature. The resulting product is a polyisocyanateprepolymer having an isocyanate equivalent weight of 588 and an acidvalue of abut 14.8.

(c) The polyisocyanate prepolymer product of part (b) immediately aboveis modified with trimethylolpropane as follows. A reaction vesselequipped as described in part (b) immediately above is charged at roomtemperature under a blanket of nitrogen with 2102 g of thepolyisocyanate prepolymer product of part (b) and the contents of thevessel are heated over a period of 30 minutes to a temperature of 65° C.at which point 130 g of methylisobutyl ketone is added to the vessel.Heating is continued at 65° C. for 4 minutes after which 32.5 g oftrimethylolpropane is added to the contents of the vessel. Thereafterthe contents of the vessel are heated over a period of 32 minutes to atemperature of 89° C. and thereafter held for 3 hours and 58 minutes ata temperature ranging from 89° C. to 93° C. after which heating isdiscontinued and the contents of the vessel allowed to cool to roomtemperature. The resulting product is a polyisocyanate prepolymer havingan isocyanate equivalent weight of 801.

(d) The aminoalkyloxy silane of part (a) immediately above in an amountof 439 g is mixed at room temperature with 667.2 g of anhydrous ethanol.To the resultant mixture is slowly added over a period of 15 minutes1400 g of the polyisocyanate prepolymer product of part (c) immediatelyabove while the temperature is maintained at less that 55° C. Theresulting resin composition has an acid value of 7.2, contains 0.04milliequivalents of amine per gram, has a Gardner-Holdt bubble tubeviscosity of 31.5 seconds, a solids content at 105° C. of 58.8 percentby weight, and a solids content at 150° C. of 54.7 percent by weight.

EXAMPLE 4

(a) A polyisocyanate prepolymer is prepared as follows. A reactionvessel equipped with heating mantle, thermometer, stirrer, refluxcondenser, and source of nitrogen is charged at room temperature under ablanket of nitrogen with 75 g of dimethylolpropionic acid, 616 g ofPCP-0300¹, 1184 g of dicyclohexylmethane-4,4'-diisocyanate, and 330 g ofmethylisobutyl ketone. The reaction mixture is heated over a period of30 minutes to a temperature of 65° C. at which point heating isdiscontinued. Thereafter the reaction mixture exotherms over a period of30 minutes to a temperature of 103° C. after which the mixture is cooledover a period of 15 minutes to a temperature of 97° C. Thereafter, thereaction mixture is held for 15 minutes in a temperature range of 97° C.to 93° C. after which an additional 130 g of methylisobutyl ketone isadded to the mixture. Thereafter, the mixture is maintained in atemperature range of 93° C. to 95° C. over a period of 2 hours and 30minutes. The resulting product is a polyisocyanate prepolymer having anisocyanate equivalent weight of 532 and an acid value of 14.6.

(b) A reaction vessel equipped with a thermometer, stirrer, refluxcondenser, and source of nitrogen is charged at room temperature under ablanket of nitrogen with 646.4 g of the aminoalkyloxy silane product ofExample 3(a) and 678 g of anhydrous ethanol. Thereafter, 1370 g of thepolyisocyanate prepolymer product of part (a) immediately above isslowly added to the contents of the vessel over a period of 25 minuteswhile the temperature is maintained at less than 55° C. Thereafter, thecontents of the vessel are allowed to cool with stirring over a periodof 8 minutes to a temperature of 42° C. Thereafter, a total of 160 g ofanhydrous ethanol is added to the contents of the vessel. The resultingresin composition has an acid value of 6.9, contains 0.046milliequivalents of amine per gram, has a Garnder-Holdt bubble tubeviscosity of 42 seconds, a solids content at 105° C. of 55.7 percent byweight, and a solids content at 150° C. of 49.5 percent by weight.

EXAMPLE 5

(a) An aminoalkyloxy silane is prepared from a 1 to 1 mole ratio of2-amino-2-methylpropanol and tetraethylorthosilicate according to aprocedure similar to the procedure for preparation of the aminoalkyloxysilane of Example 3(a). The resulting aminoalkyloxy silane has atheoretical amine equivalent weight of 251.

(b) A polyisocyanate prepolymer is prepared by reacting 139.3 g ofdimethylolpropionic acid, 1468.3 g of PCP-0200¹, and 1996.1 g ofdicyclohexylmethane-4,4'-diisocyanate (DESMODUR-W²), in 396.3 g ofmethylisobutyl ketone employing a procedure similar to those describedfor the preparation of polyisocyanate prepolymers in the previousexamples. The resulting polyisocyanate prepolymer product has anisocyanate equivalent weight of 593.6 and an acid value of about 14.8.

(c) The aminoalkyloxy silane of part (a) immediately above in an amountof 60.6 g is premixed with 8.8 g of isophorone diamine and 113 g ofanhydrous ethanol at room temperature. To the resulting composition isslowly added 200 g of the polyisocyanate prepolymer product of part (b)immediately above while maintaining the temperature of the compositionbelow 55° C. The resulting resin composition of the invention has anacid value of 8.0, contains 0.045 milliequivalents of amine per gram,has a Gardner-Holdt bubble tube viscosity of 100.8 seconds (Z-4⁺), asolids content at 105° C. of 62.3 percent by weight and a solids contentat 150° C. of 57.6 percent by weight.

(d) The aminoalkyloxy silane of part (a) immediately above in an amountof 43.3 g is premixed with 14.7 g of isophorone diamine and 107 g ofanhydrous ethanol at room temperature. To the resulting composition isslowly added 200 g of the polyisocyanate prepolymer product of part (b)immediately above while maintaining the temperature of the compositionbelow 55° C. Thereafter, an additional 50 g of anhydrous ethanol isadded to the composition. The resulting resin composition of theinvention has an acid value of 7.1, contains 0.053 milliequivalents ofamine per gram, has a Gardner-Holdt viscosity of Z-4, a solids contentat 105° C. of 56.1 percent by weight, and a solids content at 150° C. of52.4 percent by weight.

(e) The aminoalkyloxy silane of part (a) immediately above in an amountof 26.0 g is premixed with 20.5 g of isophorone diamine and 100 g ofanhydrous ethanol at room temperature. To the resulting composition isslowly added 200 g of the polyisocyanate prepolymer product of part (b)immediately above while maintaining the temperature of the compositionbelow 55° C. Thereafter, an additional 125 g of anhydrous ethanol isadded to the composition. The resulting resin composition of theinvention has an acid value of 6.2, contains 0.035 milliequivalents ofamine per gram, has a Gardner-Holdt bubble tube viscosity of 114 (Z-4⁺),a solids content at 105° C. of 47.8 percent by weight, and a solidscontent at 150° C. of 46.3 percent by weight.

EXAMPLE 6

(a) An aminoalkyloxy silane is prepared from a 1 to 1 mole ratio of2-amino-2-methylpropanol and tetraethylorthosilicate according to aprocedure similar to the procedure for preparation of the aminoalkyloxysilane of Example 3(a). The resulting aminoalkyloxy silane has atheoretical amine equivalent weight of 251.

(b) A polyisocyanate prepolymer is prepared as follows. A reactionvessel equipped with heating mantle, thermometer, stirrer, refluxcondenser, and source of nitrogen is charged at room temperature under ablanket of nitrogen with 667 g of PCP-0200¹, 46.4 g of N-methyldiethanol amine, 647.7 g of dicyclohexylmethane-4,4'-diisocyanate, and151 g of 2-ethoxyethylacetate (Cellosolve acetate). The reaction mixtureis heated to a temperature of 98° C. and thereafter held at atemperature of about 100° C. for 3 hours and 55 minutes. The resultingproduct is a polyisocyanate prepolymer having an isocyanate equivalentweight of 970.

(c) The aminoalkyloxy silane of part (a) immediately above in an amountof 155.3 g is mixed with 238 g of anhydrous ethanol. To the resultantmixture is slowly added with stirring 600 g of the polyisocyanateprepolymer product of part (b) immediately above over a period of about6 minutes while the temperature is maintained below 55° C. Thereafter,stirring is continued for approximately an additional 10 minutes. Theresulting product represents a resin of the invention.

EXAMPLE 7

(a) An aminoalkyloxy silane is prepared from a 1 to 1 mole ratio of2-amino-2-methylpropanol and tetraethylorthosilicate according to aprocedure similar to the procedure for preparation of the aminoalkyloxysilane of Example 3(a). The resulting aminoalkyloxy silane has atheoretical amine equivalent weight of 251.

(b) A polyisocyanate prepolymer is prepared by reacting 667 g ofPCP-0200¹, 40.6 of neopentyl glycol, 647.7 g ofdicyclohexylmethane-4,4'-diisocyanate, in 150 g of 2-ethoxyethylacetate(Cellosolve acetate) employing a procedure similar to that described forthe preparation of the polyisocyanate prepolymer of Example 6(b). Theresulting polyisocyanate prepolymer product has an isocyanate equivalentweight of 980.2.

(c) The aminoalkyloxy silane of part (a) immediately above in an amountof 153.7 g is mixed at room temperature with 693.7 g of anhydrousethanol. To the resultant mixture is added with stirring over a periodof about 4 minutes 600 g of the polyisocyanate prepolymer product ofpart (b) immediately above while the temperature is maintained below 55°C. Thereafter, stirring is continued for about an additional 10 minutes.The resulting product represents a resin of the invention. The productcontains 0.01 equivalents of amine per gram, has a solids content at105° C. of 46.6 percent by weight, and has a solids content at 150° C.of 44.1 percent by weight.

EXAMPLE 8

(a) An aminoalkyloxy silane is prepared from a 1 to 1 mole ratio of2-amino-2-methylpropanol and tetraethylorthosilicate according to aprocedure similar to the procedure for preparation of the aminoalkyloxysilane of Example 3(a). The resulting aminoalkyloxy silane has atheoretical amine equivalent weight of 251.

(b) A polyisocyanate prepolymer is prepared by reacting 667 g ofPCP-0200¹, 52.3 g of dimethylolpropionic acid, 647.7 g ofdicyclohexylmethane-4,4'-diisocyanate, in 152 g of 2-ethoxyethylacetate(Cellosolve acetate) employing a procedure similar to that described forthe preparation of the polyisocyanate prepolymer of Example 6(b). Theresulting polyisocyanate prepolymer product has an isocyanate equivalentweight of 1023.5.

(c) The aminoalkyloxy silane of part (a) immediately above in an amountof 147.1 g is mixed at room temperature with 234.5 g of anhydrousethanol. To the resultant mixture is added with stirring over a periodof about 4 minutes 600 g of the polyisocyanate prepolymer product ofpart (b) immediately above while the temperature is maintained below 55°C. Thereafter, stirring is continued for about an additional 10 minutes.The resulting product represents a resin of the invention. The productcontains 0.03 milliequivalents of amine per gram, has an acid value of8.6, has a solids content at 105° C. of 65.0 percent by weight and asolids content at 150° C. of 60.5 percent by weight.

EXAMPLE 9

(a) An aminoalkyloxy silane is prepared as follows. A reaction vesselequipped with heating mantle, thermometer, stirrer and distillationcolumn is charged at room temperature with a reaction mixture of 498.7 gof 2-aminoethanol and 1701 g of tetraethylorthosilicate. The reactionmixture is heated and distillate is collected according to the scheduleset forth in the following TABLE 4. The temperature of the reactionvessel and the head temperature of the distillation column are given forthe end of each corresponding time period. The amount of distillate asrepresented in each horizontal row represents the total distillatecollected up to the end of the corresponding time period (i.e.,including that collected during the preceding time period). Theresulting product is an aminoalkyloxy silane and has a theoretical amineequivalent weight of 223.

                  TABLE 4                                                         ______________________________________                                                 Temperature of                                                                            Head                                                              Reaction Vessel                                                                           Temperature Total Distillate                             Time (min)                                                                             (°C.)                                                                              (°C.)                                                                              Collected (ml)                               ______________________________________                                         0-225   113         79          140                                          255-277  112         79          205                                          277-308  126         72          305                                          308-336  131         77          345                                           0-140   148         76          425                                          140-200  158         71          465                                          ______________________________________                                         *Heating is discontinued and the reaction mixture allowed to cool.       

(b) A polyisocyanate prepolymer is prepared from the same ingredients,in the same amounts, and according to a similar procedure as forpreparation of the polyisocyanate prepolymer of Example 5(b) and ismixed with an amount of the polyisocyanate prepolymer of Example 5(b).The resulting polyisocyanate prepolymer product has an isocyanateequivalent weight of 554.3.

(c) The aminoalkyloxy silane of part (a) immediately above in an amountof 80.5 g is mixed at room temperature with 115 g of anhydrous ethanol.To the resultant mixture is added slowly with stirring 200 g of thepolyisocyanate prepolymer product of part (b) immediately above whilethe temperature is maintained below 55° C. The resulting productrepresents a resin of the invention. The product contains 0.036milliequivalents of amine per gram, has an acid value of 7.4, has aGardner-Holdt bubble tube viscosity of 6.0 seconds, has a solids contentat 105° C. of 56.9 percent by weight and a solids content at 150° C. of53.7 percent by weight.

EXAMPLE 10

(a) An aminoalkyloxy silane is prepared by reacting 344.5 g ofmonoisopropanol amine and 955.5 g of tetraethylorthosilicate accordingto a procedure similar to the procedure for preparation of theaminoalkyloxy silane of Example 3(a). A total of 265 ml of distillate iscollected. The resulting product is an aminoalkyloxy silane and has atheoretical amine equivalent weight of 237.

(b) The aminoalkyoxy silane of part (a) immediately above in an amountof 85.5 g is mixed at room temperature with 120 g of anhydrous ethanol.To the resultant mixture is added slowly with stirring 200 g of thepolyisocyanate prepolymer product of Example 9(b) while the temperatureis maintained below 55° C. The resulting product represents a resin ofthe invention. The product contains 0.052 milliequivalents of amine pergram, has an acid value of 7.1, has a Gardner-Holdt bubble tubeviscosity of 12.7 seconds, has a solids content at 105° C. of 57.4percent by weight and a solids content at 150° C. of 54.6 percent byweight.

EXAMPLE 11

This example illustrates the preparation of a resin of the inventioncorresponding to formula (I) in which R¹ represents the radical##STR13##

(a) A reaction vessel equipped with stirrer and means for cooling thecontents of the vessel is charged at room temperature with 223 g of theaminoalkyloxy silane prepared in Example 9(a). Thereafter, 100 g ofethyl acrylate is added dropwise with stirring over a period of 35minutes to the contents of the vessel while the temperature ismaintained in the range of from 20° C. to 35° C. Thereafter, thecontents of the vessel are stirred for 1 hour. The resulting product hasa theoretical amine equivalent weight of 323.

(b) The reaction product of part (a) immediately above in an amount of116.5 g is mixed at room temperature with 135 g of anhydrous ethanol. Tothe resultant mixture is added slowly with stirring 200 g of thepolyisocyanate prepolymer product of Example 9(b) while the temperatureis maintained below 55° C. The resulting product represents a resin ofthe invention. The product contains 0.082 milliequivalents of amine pergram, has a Gardner-Holdt bubble tube viscosity of 5.0 seconds, has anacid value of 6.3, has a solids content at 105° C. of 58.5 percent byweight and a solids content at 150° C. of 53.4 percent by weight.

EXAMPLE 12

(a) An aminoalkyloxy silane is prepared from 359.6 g of2-amino-2-methylpropanol and 840.4 g of tetraethylorthosilicateaccording to a procedure similar to the procedure for preparation of theaminoalkyloxy silane of Example 3(a). A total of 233 ml of distillate iscollected. The resulting aminoalkyloxy silane has a theoretical amineequivalent weight of 251.

(b) A polyisocyanate prepolymer is prepared as follows. A reactionvessel equipped with heating mantle, thermometer, stirrer, and refluxcondenser is charged at room temperature with 77.3 g ofdimethylolpropionic acid, 815 g of PCP-0200¹, and 1108 g ofdicyclohexylmethane-4,4'-diisocyanate (DESMODUR-W). The reaction mixtureis heated over a period of 90 minutes to a temperature of 78° C. afterwhich heating is discontinued. The temperature continues to rise overthe next 10 minutes to 140° C. after which the reaction mixture iscooled over the next 14 minutes to 90° C. Thereafter, the temperature ofthe reaction mixture rises and is maintained at about 98° C. over aperiod of 261 minutes. The resulting product is a polyisocyanateprepolymer having an isocyanate equivalent weight of 536.9.

(c) Three resins of the invention herein designated 12A, 12B and 12Crespectively are prepared as follows. Three reaction vessels are chargedwith the ingredients set forth in TABLE 5 under "Charge 1". Thereafter,to each of the reaction vessels is slowly added with stirring thepolyisocyanate prepolymer product of part (b) immediately above in theamounts set forth in TABLE 5 under "Charge 2" while the temperature ofthe contents of the vessels is maintained at about 80° C. to about 90°C. The milliequivalents (meq) of amine per gram, Gardner-Holdt bubbletube viscosity, and solids contents at 105° C. and 150° C. of each ofthe resulting resin products A, B and C are as set forth in TABLE 5.

                  TABLE 5                                                         ______________________________________                                                           Weight (g)                                                                    A     B       C                                            ______________________________________                                        Charge 1                                                                      Anhydrous ethanol    150     150     150                                      Gamma-aminopropyltrimethoxysilane                                                                  53.5    28.8    0                                        Aminoalkyloxy silane.sup.2                                                                         32.7    60.8    93.5                                     Charge 2                                                                      Polyisocyanate prepolymer.sup.3                                                                    200     200     200                                      Meq amine/gram       0.016   0.062   0.020                                    Gardner-Holdt viscosity (seconds)                                                                  18.1    28.5    50.7                                     Solids Content (2 hours/105° C.)                                                            62.5    63.3    67.3                                     Solids Content (2 hours/150° C.)                                                            59.4    60.2    60.1                                     ______________________________________                                         .sup.2 The aminoalkyloxy silane of Example 12 (a)                             .sup.3 The polyisocyanate prepolymer product of Example 12 (b).          

(d) Each of the resins A, B and C of part (c) immediately above is drawndown to a wet film thickness of 4 mils on steel panels and cured at 250°F. (121° C.) for 30 minutes. Each of the resulting cured films is clearand hard.

EXAMPLE 13

(a) A composition containing perethyldisilicate is prepared as follows.A reaction flask equipped with thermometer, stirrer, condenser, andsource of nitrogen is charged under a blanket of nitrogen with 14,400 gof tetraethylorthosilicate, 2,880 g of ethyl alcohol, and 0.864 g of a37 percent by weight solution of hydrochloric acid. Thereafter, 482.4 gof deionized water is slowly added with stirring to the contents of thereaction flask over a period of 82 minutes after which stirring iscontinued for an additional 48 minutes. The resulting compositioncontains perethyl disilicate, has a residual water content of 0.07percent by weight, and has a solids content at 105° C. of 7.3 percent byweight.

(b) An aminoalkyloxy silane is prepared as follows. A reaction vesselequipped with heating mantle, thermometer, stirrer, and distillationcolumn is charged at room temperature with 190.6 g of2-amino-2-methylpropanol and 1109.8 g of the composition containingperethyldisilicate of part (a) immediately above. The reaction mixtureis heated and distillate is collected according to the schedule setforth in the following TABLE 6. The temperature of the reaction vesseland the head temperature of the distillation column are given for theend of each corresponding time period. The amount of distillate in eachhorizontal row represents the total distillate collected up to the endof the corresponding time period (i.e., including that collected duringthe preceding time period). The resulting product is an aminoalkyloxysilane and has a theoretical amine equivalent weight of 385.

                  TABLE 6                                                         ______________________________________                                                 Temperature of                                                                            Head                                                              Reaction Vessel                                                                           Temperature Total Distillate                             Time (min)                                                                             (°C.)                                                                              (°C.)                                                                              Collected (ml)                               ______________________________________                                        0-80      89         77           85                                          80-135    90         76          305                                          0-60     135         79          505                                          60-107   147         76          600                                          ______________________________________                                         *Heating is discontinued and the reaction mixture allowed to cool.       

(c) A polyisocyanate prepolymer is prepared by reacting 77.3 g ofdimethylolpropionic acid, 815 g of PCP-0200¹, and 1108 g ofdicyclohexylmethane-4,4'-diisocyanate (DESMODUR-W) in 220 g ofmethylisobutyl ketone according to a procedure similar to the procedurefor preparation of the polyisocyanate prepolymer of Example 1(b). Theresulting polyisocyanate prepolymer product has an isocyanate equivalentweight of 578.6 and an acid value of 14.6.

(d) The aminoalkyloxy silane of part (b) immediately above in an amountof 99.6 g is mixed at room temperature with 110 g of anhydrous ethanol.To the resultant mixture is added slowly with stirring 150 g of thepolyisocyanate prepolymer product of part (c) immediately above whilethe temperature is maintained below 55° C. The resulting productrepresents a resin of the invention. The product contains 0.748milliequivalents of amine per gram, has a Gardner-Holdt bubble tubeviscosity of 14.2 seconds, has an acid value of 5.9, has a solidscontent at 105° C. of 58.1 percent by weight and a solids content at150° C. of 51.5 percent by weight.

EXAMPLE 14

(a) An aminoalkyloxy silane is prepared as follows. A reaction vesselequipped with heating mantle, thermometer, stirrer, and distillationcolumn is charged at room temperature with a reaction mixture of 133 gof diisopropanol amine and 416 g of tetraethylorthosilicate. Thereaction mixture is heated and distillate is collected according to theschedule set forth in the following TABLE 7. The temperature of thereaction vessel and the head temperature of the distillation column aregiven for the end of each corresponding time period. The amount ofdistillate in each horizontal row represents the total distillatecollected up to the end of the corresponding time period (i.e.,including that collected during the preceding time period). Theresultant product is an aminoalkyloxy silane and has a theoretical amineequivalent weight of 457.

                  TABLE 7                                                         ______________________________________                                                 Temperature of                                                                            Head                                                              Reaction Vessel                                                                           Temperature Total Distillate                             Time (min)                                                                             (°C.)                                                                              (°C.)                                                                              Collected (ml)                               ______________________________________                                         0-180   116         72          40                                           180-195  116         72          50                                            0-60    121         72          60                                           60-90    150         74          84                                            90-130  172         74          95                                           130-167  187         50          115                                          ______________________________________                                         *Heating is discontinued and the reaction mixture allowed to cool.       

(b) The aminoalkyloxy silane of part (a) immediately above in an amountof 118.2 g is mixed at room temperature with 120 g of anhydrous ethanol.To the resultant mixture is added slowly with stirring 150 g of thepolyisocyanate prepolymer product of Example 13(c) while the temperatureis maintained below 55° C. The resulting product represents a resin ofthe invention. The product contains 0.536 milliequivalents of amine pergram, has a Gardner-Holdt bubble tube viscosity of 22.5 seconds, has anacid value of 6.1, has a solids content of 105° C. of 55.5 percent byweight and a solids content of 150° C. of 50.1 percent by weight.

What is claimed is:
 1. An ungelled resin comprising a compoundcorresponding to the formula, ##STR14## wherein Q represents the residueof an organic isocyanate having an average isocyanate functionality ofat least 1,R¹ independently represents H, a C₁ to C₁₀ alkyl radical, aC₁ -C₁₀ hydroxyalkyl radical or a radical corresponding to the formula##STR15## wherein Z represents H or C₁ to C₄ alkyl, and W represents##STR16## in which R⁸ represents C₁ to C₈ alkyl, X represents a divalentradical containing at least 2 carbon atoms, A represents a monovalentsilicon-containing group corresponding to the formula ##EQU2## whereinR² independently represents hydrogen, a C₁ to C₁₀ alkyl group, a C₄ toC₁₀ cycloalkyl group, a C₆ to C₁₀ aryl group, or a monovalent aminoalkylgroup, that is attached directly to Si, Y represents a hydrolyzablegroup that is attached directly to Si, m is an integer ranging from 1 to5, e is a positive integer wherein 1≦e≦11, d is zero or a positiveinteger wherein 0≦d≦10, and 3≦d+e≦11, and wherein x is a positive numberwhich is equal to or less than the average isocyanate functionality ofsaid organic isocyanate.
 2. The resin of claim 1 wherein saidhydrolyzable group Y is selected from the group consisting of ##STR17##and the C₂ to C₃ residue of a 1,2- or 1,3-glycol, whereinR³ representsC₁ -C₇ alkyl, C₆ -C₈ cycloalkyl, C₆ -C₈ aryl, or C₃ -C₈ alkoxyalkyl, R⁴represents H or C₁ -C₄ alkyl, R⁵ and R⁶ independently represent C₁ -C₄alkyl, C₆ -C₈ cycloalkyl, or C₆ -C₈ aryl, and R⁷ represents C₄ -C₇alkylene.
 3. The resin of claim 2 wherein Q represents the residue froman isocyanate-functional polyisocyanate which is a reaction product ofan organic polyisocyanate and a polyol having an average molecularweight ranging from 62 to about 3,000.
 4. The resin of claim 3 whereinsaid polyol comprises a polyester polyol having an average molecularweight ranging from about 170 to about 2,000.
 5. The resin of claim 4wherein R¹ represents hydrogen.
 6. The resin of claim 1 wherein saidpolyol comprises a polyol containing at least one carboxylic acid group.7. The resin of claim 1 which is essentially free of isocyanateradicals.
 8. The resin of claim 1 wherein said monovalentsilicon-containing group contains at least 2 of said hydrolyzable groupsY which may be the same or different.
 9. The resin of claim 1 wherein Qrepresents the residue from an isocyanate-functional polyisocyanateprepolymer which is a reaction product of an organic polyisocyanate anda polyol, which polyol has an average molecular weight ranging from 62to about 3,000; R¹ represents hydrogen; A represents a monovalentsilicon-containing group from an organosilicate and d equals zero. 10.The resin of claim 9 wherein said polyol comprises a polyol containingat least one carboxylic acid group.
 11. A coating composition comprisingan ungelled resin containing a compound corresponding to the formula,##STR18## wherein Q represents the residue of an organic isocyanatehaving an average isocyanate functionality of at least 1,R¹ representsH, a C₁ to C₁₀ alkyl radical, a C₁ -C₁₀ hydroxyalkyl radical or aradical corresponding to the formula ##STR19## wherein Z represents H orC₁ to C₄ alkyl, and W represents ##STR20## in which R⁸ represents C₁ toC₈ alkyl, X represents a divalent radical containing at least 2 carbonatoms, A represents a monovalent silicon-containing group correspondingto the formula ##EQU3## wherein R² independently represents hydrogen, aC₁ to C₁₀ alkyl group, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ arylgroup, or a monovalent aminoalkyl group, that is attached directly toSi, Y represents a hydrolyzable group that is attached directly to Si mis an integer ranging from 1 to 5, e is a positive integer wherein1≦e≦11 d is zero or a positive integer wherein 0≦d≦10, and 3≦d+e≦11,andwherein x is a positive number which is equal to or less than theaverage isocyanate functionality of said organic isocyanate.
 12. Thecoating composition of claim 11 wherein Q represents the residue from anisocyanate-functional polyisocyanate which is a reaction product of anorganic polyisocyanate and a polyol having an average molecular weightranging from 62 to about 3,000.
 13. The coating composition of claim 11wherein said polyol comprises a polyol containing at least onecarboxylic acid group.
 14. The coating composition of claim 11 whereinsaid resin is essentially free of isocyanate radicals.
 15. The coatingcomposition of claim 11 where in said resin, Q represents the residuefrom an isocyanate-functional polyisocyanate which is a reaction productof an organic polyisocyanate and a polyol, which polyol has an averagemolecular weight ranging from 62 to 3,000; R¹ represents hydrogen; and Arepresents a monovalent silicon-containing group from an organosilicateand d equals zero.
 16. The coating composition of claim 15 wherein saidpolyol comprises a polyol containing at least one carboxylic acid group.17. The coating composition of claim 11 additionally comprising acure-promoting catalyst.
 18. The coating composition of claim 11additionally comprising a polyol.
 19. A two pack coating composition, afirst pack comprising an ungelled resin containing a compound accordingto the formula, ##STR21## wherein Q represents the residue of an organicisocyanate having an average isocyanate functionality of at least 1,R¹independently represents H or a C₁ to C₁₀ alkyl radical, a C₁ -C₁₀hydroxyalkyl radical or a radical corresponding to the formula ##STR22##wherein Z represents H or C₁ to C₄ alkyl, and W represents ##STR23## inwhich R⁸ represents C₁ to C₈ alkyl, X represents a divalent radicalcontaining at least 2 carbon atoms, A represents a monovalentsilicon-containing group corresponding to the formula ##EQU4## whereinR² independently represents hydrogen, a C₁ to C₁₀ alkyl group, a C₄ toC₁₀ cycloalkyl group, a C₆ to C₁₀ aryl group, or a monovalent aminoalkylgroup, that is attached directly to Si, Y represents a hydrolyzablegroup that is attached directly to Si m is an integer ranging from 1 to5, e is a positive integer wherein 1≦e≦11, d is zero or a positiveinteger wherein 0≦d≦10, and 3d+e≦11, andwherein x is a positive numberwhich is equal to or less than the average isocyanate functionality ofsaid organic isocyanate; and a second pack comprising a cure-promotingcatalyst.
 20. The two pack coating composition of claim 19 where forsaid resin, Q represents the residue from an isocyanate-functionalpolyisocyanate which is a reaction product of an organic polyisocyanateand a polyol, which polyol has an average molecular weight ranging from62 to about 3,000; R¹ represents hydrogen, and A represents a monovalentsilicon-containing group from an organosilicate and d equals zero. 21.The two-pack coating composition of claim 20 wherein said polyolcomprises a polyol containing at least one carboxylic acid group. 22.The ungelled resin of claim 1 wherein X represents a divalent radicalcontaining at least 2 carbon atoms containing one or more groupsselected from ether, amino, amido, carbamate, urea, and thio.
 23. Thecoating composition of claim 11 wherein X represents a divalent radicalcontaining at least 2 carbon atoms containing one or more groupsselected from ether, amino, amido, carbamate, urea, and thio.
 24. Thetwo pack coating composition of claim 19 wherein X represents a divalentradical containing at least 2 carbon atoms containing one or more groupsselected from ether, amino, amido, carbamate, urea, and thio.